CN107754782B - Self-supporting VO2Preparation method and product of Fenton-like catalytic material - Google Patents
Self-supporting VO2Preparation method and product of Fenton-like catalytic material Download PDFInfo
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- CN107754782B CN107754782B CN201710959261.XA CN201710959261A CN107754782B CN 107754782 B CN107754782 B CN 107754782B CN 201710959261 A CN201710959261 A CN 201710959261A CN 107754782 B CN107754782 B CN 107754782B
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims description 25
- 238000001354 calcination Methods 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
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- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
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- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 27
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B01J35/397—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention belongs to the field of catalyst preparation, and particularly discloses a self-supporting VO2The preparation method of the Fenton-like catalytic material and the product thereof comprise the following steps: (1) preparation V2O5Sol and aging; (2) immersing the anode and cathode conductive substrates in V2O5Electrophoretic deposition is carried out in the sol to obtain V2O5A coated conductive substrate; (3) v prepared in the step (2)2O5Placing the coated conductive substrate in a tubular furnace, calcining under the condition of ventilation atmosphere, wherein the temperature rise rate of the calcination is 1-20 ℃/min, the calcination temperature is 600-1000 ℃, the heat preservation time is 0.5-10h, and the introduction speed of the atmosphere is 0.1-10L/min, thereby obtaining the self-supporting VO2A fenton-like catalytic material. VO prepared by the invention2The Fenton-like catalytic material has excellent self-supporting property and catalytic performance, has no secondary pollution to the environment, and can realize low-cost and large-scale production.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a self-supporting VO2A preparation method of Fenton-like catalytic material and a product.
Background
In recent years, the global water pollution crisis is continuously intensified, organic dyes such as textiles and dyes and phenolic compounds are main components of wastewater, Advanced Oxidation Processes (AOPs) are an effective method for decomposing and synthesizing organic pollutants, Fenton-like catalytic materials are effective advanced oxidation catalysts, and novel Fenton-like catalytic materials attract attention.
The vanadium dioxide (VO) has rich reserves, low price and easy obtainment and unique advantages in practical application2) Is widely used in the manufacture of optical devices and electronic devices, but there are few reports on the use of Fenton catalysts for the degradation of organic substances. For VO to realize effective utilization of vanadium2The research of the Fenton-like catalytic material has important scientific significance and practical value.
Disclosure of Invention
In view of the above-mentioned drawbacks or needs of improvement of the prior art, it is an object of the present invention to provide a self-supporting VO2The Fenton-like catalytic material and the preparation method thereof have the characteristics of simplicity, rapidness and high efficiency, and the obtained VO2The Fenton-like catalytic material has self-supporting properties.
To achieve the above object, according to one aspect of the present invention, there is provided a self-supporting VO2The preparation method of the Fenton-like catalytic material comprises the following steps of:
(1) preparing V with mass volume concentration of 5g/L-40g/L2O5Sol, aging for 1-15 days;
(2) immersing cathode conductive substrate anode and cathode into V in step (1)2O5Performing electrophoretic deposition in the sol to deposit V on the surface of the conductive substrate2O5Thereby obtaining V2O5The voltage of electrophoretic deposition of the coated substrate is 0.001-10V, the distance between an anode and a cathode is 5-50mm, and the deposition time is 0.5-60 min;
(3) v prepared in the step (2)2O5The coated conductive base material is placed in a tubular furnace and calcined under the condition of ventilation atmosphere, wherein the temperature rise rate of the calcination is 1-20 ℃/min, the calcination temperature is 600-1000 ℃, the heat preservation time is 0.5-10h, the atmosphere introduction speed is 0.1-10L/min, the whole heat treatment process is effectively carried out in the protective atmosphere through the calcination process, and the surface of the base material is ensured to be onV of parcel2O5The sol was fully melted.
By the method, the self-supporting VO with the core-shell structure can be obtained2A fenton-like catalytic material.
Further preferably, V is2O5The sol is prepared by first preparing V2O5The powder is heated to a molten state and then deionized water is added for preparation.
Further preferably, V is2O5The purity of the powder is more than 99%.
More preferably, the voltage of the electrophoretic deposition is 0.002-2.5V, the distance between the anode and the cathode is 10-30mm, and the deposition time is 2-10 min.
More preferably, the atmosphere is nitrogen gas having a purity of 99% or more.
Preferably, the temperature rise rate of the calcination is 5-10 ℃/min, the calcination temperature is 700-800 ℃, the heat preservation time is 2-3 h, and the introduction speed of the atmosphere is 0.5-1L/min.
Further preferably, the conductive substrate is a conductive material which is flexible and can resist a high temperature of 600 ℃ or higher.
Further preferably, the conductive substrate is an iron mesh or an iron steel mesh.
Further preferably, the anode is a platinum sheet, a gold sheet or graphite.
According to another aspect of the present invention, there is provided a self-supporting VO2Fenton-like catalytic material prepared by the preparation method.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. the invention combines the electrophoretic deposition technology and the high-temperature calcination technology, realizes the self-supporting VO which is simple, rapid, efficient and suitable for large-scale production2The Fenton-like catalytic material is prepared, and the preparation process is simple, environment-friendly and pollution-free.
2. The invention is to self-supporting VO2A great deal of research is carried out on the specific preparation process of the Fenton-like catalytic material,particularly, the research of the calcining process obtains the following better calcining process that the calcining temperature rise rate is 1-20 ℃/min, the calcining temperature is 600-2A fenton-like catalytic material.
3. The invention further researches the calcination process to obtain the following best VO prepared by the invention through the mutual cooperation and comprehensive action of the process parameters that the temperature rise rate of the calcination process is 5-10 ℃/min, the calcination temperature is 700-800 ℃, the heat preservation time is 2-3 h, the atmosphere introduction speed is 0.5-1L/min2The Fenton-like catalytic material has optimal performance, and the prepared VO2Surface VO of Fenton-like catalytic material2The catalyst has good crystallinity, uniform crystal grain size, uniform covering on the substrate and good effect of catalyzing organic dye.
4. The invention also researches the technological parameters of the deposition reaction, and the uniform V is coated on the surface of the base material under the interaction and the cooperation of the technological parameters of 0.002-2.5V of voltage, 10-30mm of distance between the anode and the cathode and 2-10 min of deposition time2O5And (3) sol.
5. VO prepared by the invention2The Fenton-like catalytic material has excellent self-supporting characteristic and catalytic performance, and compared with the traditional powdery nano-particle or nano-fiber catalyst, the VO prepared by the method provided by the invention2The Fenton-like catalytic material is convenient to separate, recover and reuse after the catalytic reaction is finished, can effectively catalyze and degrade organic dye, has no secondary pollution to the environment, and can realize low-cost and large-scale production.
Drawings
FIG. 1 is a self-supporting VO of the present invention2A flow chart of Fenton-like catalytic material preparation;
FIG. 2 is a self-supporting VO of the present invention2XRD spectrum of Fenton-like catalytic material;
FIG. 3 is a self-supporting VO prepared in example 12SEM photograph of Fenton-like catalytic material;
FIG. 4 is a self-supporting VO prepared in example 22SEM photograph of Fenton-like catalytic material;
FIG. 5 is a self-supporting VO prepared in example 32SEM photograph of Fenton-like catalytic material;
FIG. 6 is a self-supporting VO prepared in example 42SEM photograph of Fenton-like catalytic material;
FIG. 7 is a self-supporting VO prepared in example 32The catalytic performance of the Fenton-like catalytic material and a comparison experiment result chart;
FIGS. 8(a) - (d) are self-supporting VOs prepared in example 32The structure of the Fenton-like catalytic material is shown schematically.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, a self-supporting VO provided by the embodiment of the present invention2A method of fenton-like catalytic material comprising the steps of:
(1) preparation V2O5Sol with the mass volume concentration of 5g/L-40g/L is prepared and then aged for 1-15 days, so that stable sol solution is obtained;
(2) immersing a cathode conductive base material and an anode platinum sheet into the V obtained in the step (1)2O5Performing electrophoretic deposition in the sol, setting the voltage of the electrophoretic deposition to be 0.001-10V, the distance between the anode and the cathode to be 5-50mm, and the deposition time to be 0.5-60 min, so as to deposit V on the surface of the conductive substrate2O5Thereby obtaining V2O5A coated conductive substrate, preferably a conductive material which is flexible and resistant to high temperatures of 600 ℃ or higher, more preferably an iron mesh or an iron and steel mesh, such as 321L stainless steel material;
(3) mixing V prepared in step (2)2O5Placing the coated conductive substrate sample in a tubular furnace, calcining under the condition of ventilation atmosphere, setting the heating rate to be 1-20 ℃/min, the calcining temperature to be 600-2O5→4VO2+O2Then self-supporting VO is obtained2A fenton-like catalytic material.
Preferably, V2O5The sol is prepared by first preparing V2O5The powder is heated to a molten state and then deionized water is added for preparation.
Preferably, V2O5The purity of the powder is 99% or more.
Preferably, the firing atmosphere is nitrogen gas having a purity of 99% or more.
The following are specific examples of the present invention.
Example 1:
as shown in FIG. 1, first, V is set2O5Heating the powder to a molten state, and preparing V by a water quenching method2O5Sol with the concentration of 10g/L is aged for 3 days; mounting a circular steel mesh as a cathode and a platinum sheet as an anode into an electrophoretic deposition device, immersing into sol, setting the voltage of a direct current power supply to be 0.001V, the distance between electrodes to be 10mm, and the deposition time to be 10min to obtain V2O5A coated steel mesh substrate; placing the prepared sample in a tubular furnace, setting the heating rate to be 3 ℃/min, the calcining temperature to be 700 ℃, keeping the temperature for 1h, and calcining under the condition of introducing the atmosphere with the flow of 1L/min to obtain VO2A fenton-like catalytic material. The SEM photograph of the catalytic material prepared in this example is shown in FIG. 3.
Example 2:
as shown in FIG. 1, first, V is set2O5Heating the powder to a molten state, and preparing V by a water quenching method2O5Sol with the concentration of 10g/L is aged for 3 days; mounting a circular steel mesh as a cathode and a platinum sheet as an anode into an electrophoretic deposition device, immersing into sol, setting the voltage of a direct current power supply to be 0.001V, the distance between electrodes to be 10mm, and the deposition time to be 10min to obtain V2O5A coated steel mesh substrate. The prepared samplePlacing in a tube furnace, setting the heating rate at 3 ℃/min, the calcining temperature at 700 ℃, keeping the temperature for 2h, and calcining under the atmosphere condition of the flow of 1L/min to obtain VO2A fenton-like catalytic material. The SEM photograph of the catalytic material prepared in this example is shown in FIG. 4.
Example 3:
as shown in FIG. 1, first, V is set2O5Heating the powder to a molten state, and preparing V by a water quenching method2O5Sol with the concentration of 10g/L is aged for 3 days; mounting a circular steel mesh as a cathode and a platinum sheet as an anode into an electrophoretic deposition device, immersing into sol, setting the voltage of a direct current power supply to be 0.001V, the distance between electrodes to be 10mm, and the deposition time to be 10min to obtain V2O5A coated steel mesh substrate; placing the prepared sample in a tubular furnace, setting the heating rate to be 3 ℃/min, the calcining temperature to be 700 ℃, the heat preservation time to be 3h, and calcining under the condition of introducing the atmosphere with the flow of 1L/min to obtain VO2A fenton-like catalytic material. The SEM photograph of the catalytic material prepared in this example is shown in FIG. 5.
Example 4:
as shown in FIG. 1, first, V is set2O5Heating the powder to a molten state, and preparing V by a water quenching method2O5Sol with the concentration of 10g/L is aged for 3 days; mounting a circular steel mesh as a cathode and a platinum sheet as an anode into an electrophoretic deposition device, immersing into sol, setting the voltage of a direct current power supply to be 0.001V, the distance between electrodes to be 10mm, and the deposition time to be 10min to obtain V2O5A coated steel mesh substrate; placing the prepared sample in a tubular furnace, setting the heating rate to be 3 ℃/min, the calcining temperature to be 700 ℃, keeping the temperature for 4h, and calcining under the condition of introducing the atmosphere with the flow of 1L/min to obtain VO2A fenton-like catalytic material. The SEM photograph of the catalytic material prepared in this example is shown in FIG. 6.
Example 5:
as shown in FIG. 1, first, V is set2O5Heating the powder to a molten state, and preparing V by a water quenching method2O5Sol with the concentration of 15g/L is aged for 15 days; the round steel mesh is used as a cathode, and the gold sheet is used as an anodeLoading into electrophoretic deposition equipment, soaking in sol, setting DC power supply voltage at 1.5V, electrode distance at 15mm, and deposition time at 5min to obtain V2O5A coated steel mesh substrate; placing the prepared sample in a tubular furnace, setting the heating rate to be 5 ℃/min, the calcining temperature to be 680 ℃, keeping the temperature for 3h, and calcining under the condition of introducing the atmosphere with the flow of 1.5L/min to obtain VO2A fenton-like catalytic material.
Example 6:
as shown in FIG. 1, first, V is set2O5Heating the powder to a molten state, and preparing V by a water quenching method2O5Sol with the concentration of 30g/L is aged for 5 days; mounting a circular steel mesh as a cathode and a platinum sheet as an anode into an electrophoretic deposition device, immersing into sol, setting the voltage of a direct current power supply to be 0.005V, the distance between electrodes to be 20mm, and the deposition time to be 15min to obtain V2O5A coated steel mesh substrate; placing the prepared sample in a tube furnace, setting the heating rate to be 10 ℃/min, the calcining temperature to be 800 ℃, the heat preservation time to be 2h, and calcining under the condition of introducing the atmosphere with the flow of 0.5L/min to obtain VO2A fenton-like catalytic material.
Example 7:
as shown in FIG. 1, first, V is set2O5Heating the powder to a molten state, and preparing V by a water quenching method2O5Sol with the concentration of 5g/L is aged for 10 days; mounting a circular steel net as a cathode and graphite as an anode into an electrophoretic deposition device, immersing into sol, setting the voltage of a direct current power supply to be 5V, the distance between electrodes to be 50mm, and the deposition time to be 0.5min to obtain V2O5A coated steel mesh substrate; placing the prepared sample in a tube furnace, setting the heating rate at 20 ℃/min, the calcining temperature at 1000 ℃, the heat preservation time at 0.5h, and calcining under the condition of introducing the atmosphere with the flow of 10L/min to obtain VO2A fenton-like catalytic material.
Example 8:
as shown in FIG. 1, first, V is set2O5Heating the powder to a molten state, and preparing V by a water quenching method2O5Sol with the concentration of 40g/L is aged for 1 day; using a circular steel net asMounting cathode and platinum sheet as anode in electrophoretic deposition equipment, soaking in sol, setting DC power supply voltage at 0.05V, inter-electrode distance at 5mm, and deposition time at 60min to obtain V2O5A coated steel mesh substrate; placing the prepared sample in a tubular furnace, setting the heating rate to be 1 ℃/min, the calcining temperature to be 600 ℃, the heat preservation time to be 10h, and calcining under the condition of introducing the atmosphere with the flow of 0.1L/min to obtain VO2A fenton-like catalytic material.
The following focus is given to the analysis of the process and the VO obtained in connection with examples 1-42The Fenton-like catalytic material.
FIG. 2 shows VO prepared in examples 1 to 42XRD pattern of Fenton-like catalytic material. From the XRD analysis results, it can be seen that the diffraction characteristic peak corresponds to the component VO2，Fe，V2O5，Fe3O4And the main component is VO2。
FIGS. 3 to 6 show VO obtained at different times from 1h to 4h in examples 1 to 4, respectively2SEM photograph of fenton-like catalytic material. As can be seen from the figure, the surface appearance of the catalytic material changes with different heat treatment time, and when the heat treatment time is 1h, the crystal grains are not completely molded; along with the increase of the heat treatment time to 3h, the surface crystal grains of the catalytic material are clear, and the crystallization degree is good; when the heat treatment is carried out for 4 hours, clear crystal grains are reduced, and the phenomenon of overburning occurs.
FIG. 7 is a graph of the catalytic performance of the catalytic material prepared in example 3 and the results of comparative experiments. VO thus prepared2The catalytic performance of the Fenton-like catalytic material is characterized by degradation of a rhodamine B (RhB) solution. The specific experimental process is as follows: VO is introduced into a reactor2The Fenton-like catalytic material is put into a container containing 10mL of RhB (2.5 × 10)-5mol/L) solution in a beaker, followed by addition of H2O2The RhB concentration was measured every 30min with an ultraviolet-visible spectrophotometer (Mapada, UV-6100). From FIG. 7, it can be seen that only VO was added2Fenton-like catalytic material or H2O2Only a small amount of organic dye can be degraded at 140min, while VO2Fenton-like catalytic material and H2O2When the dye exists in the solution, more than 90 percent of the organic dye RhB is successfully degraded within 140 min.
FIGS. 8(a) - (d) are self-supporting VOs prepared in example 32The structure of the Fenton-like catalytic material is shown schematically. As can be seen from FIG. 8, the catalytic material prepared by the present invention has a core-shell structure, such that VO of the present invention is provided2The Fenton-like catalytic material has good self-supporting characteristics. Compared with the traditional nano particles for catalyzing organic dyes and powdery catalytic materials such as nano fibers, the catalytic material disclosed by the invention has the advantages that the separation process of the catalytic material from an organic solution and the recycling process of the catalyst are greatly simplified after the catalytic reaction is finished.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. Self-supporting VO2Use of a Fenton-like catalytic material as a Fenton-like catalyst for degrading organic dyes, characterized in that the self-supporting VO is2The Fenton-like catalytic material is prepared by the following steps:
(1) preparing V with mass volume concentration of 5g/L-40g/L2O5Sol, aging for 1-15 days;
(2) immersing a cathode conductive substrate and an anode into V of the step (1)2O5Performing electrophoretic deposition in the sol to deposit V on the surface of the conductive substrate2O5Thereby obtaining V2O5The voltage of the electrophoretic deposition of the coated conductive substrate is 0.001-10V, the distance between the anode and the cathode is 5-50mm, and the deposition time is 0.5-60 min;
(3) v prepared in the step (2)2O5Placing the coated conductive substrate in a tubular furnace, calcining under the condition of ventilation atmosphere, wherein the temperature rise rate of the calcination is 1-20 ℃/min, the calcination temperature is 600-1000 ℃, the heat preservation time is 0.5-10h, and the introduction speed of the atmosphere is 0.1-10L/min, so as to obtain the self-supporting VO2A fenton-like catalytic material.
2. As claimed in claim1, the use of the compound of formula (I), wherein V is2O5The sol is prepared by first preparing V2O5The powder is heated to a molten state and then deionized water is added for preparation.
3. The use of claim 2, wherein V is2O5The purity of the powder is more than 99%.
4. The use according to claim 1, wherein the voltage of the electrophoretic deposition is 0.002-2.5V, the distance between the anode and the cathode is 10-30mm, and the deposition time is 2-10 min.
5. Use according to claim 1, wherein the atmosphere is nitrogen with a purity of 99% or more.
6. The method as claimed in claim 1, wherein the temperature increase rate of the calcination is 5-10 ℃/min, the calcination temperature is 700-800 ℃, the holding time is 2-3 h, and the introduction speed of the atmosphere is 0.5-1L/min.
7. The use of claim 4, wherein the conductive substrate is a conductive material that is flexible and resistant to temperatures above 600 ℃.
8. The use of claim 7, wherein the conductive substrate is an iron or steel mesh.
9. Use according to any one of claims 1 to 8, wherein the anode is a platinum sheet, gold sheet or graphite.
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| CN103403925A (en) * | 2010-10-15 | 2013-11-20 | 华盛顿大学商业中心 | V2o5 electrodes with high power and energy densities |
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| CN102534731A (en) * | 2012-01-21 | 2012-07-04 | 中国科学技术大学 | Method for preparing vanadium dioxide film through electrophoretic deposition |
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